Sulfonic-acid salt and process of making same.



Nrrm) STATES I PATENT OFFICE.

LUDWIG OTTO witness, on HAMBURG, GERMANY, ASSIGNOR T IGH'IHYOL eEsELLsoHAFr, OORDES, HERMANNI a co.

SU LFONIC- ACID SALT AN D PROCESS OF MAKING SAM E.

SPECIFICATION formingpart of Letters Patent No. 671,135, dated April 2, 1901. Application filed. July 21, 1899. Serial No. 724,713. (Specimens) To all whom it ntcty concern: salts of which are soluble in water. These Be it known that I, LUDWIG OTTO HELMERS, acids and their respective alkaline-earth and a subject of the German Emperor, residing heavy-metal salts may be easily obtained if at Hamburg, in the German Empire, have inthe sulfonized product obtained from the re- 5 vented certain new and usefullmprovements action' of sulfuric acid upon sulfureted hydroin Sulfonic -Acid Salts of Alkaline Earthy carbons is neutralized in an aqueous solution Metals and Metals Proper and Their Sulfonic with the oxid, hydroxid, or carbonate of an Acids andProcesses of MakingSame,of which alkaline earth or heavy metal and after a the following isaspecification. certain. time the liquid decanted from the 10 By the specifications of the United States precipitate, then the acid in the solution set Patents Nos. 318,663 and 495,343 it has been free therefrom by precipitating the base, and disclosed that the sulfonized product obtained finally evaporating the filtrate. The so-obby the action of sulfuric acid on sulfureted tained sulfonic acids, which form soluble hydrocarbons and neutralized by means of alkaline-earth andheavy-metal salts, are dis- 15 an alkali is soluble in water. In the specifitinguished bytheir high percentage in sulcation of myUnited StatesPatentNo. 525,784 fur, (they contain generally twenty-one per I have furthermore set forth that this sulfoncent. of sulfur as against fifteen per cent. in ized product neutralized by means of alkalies the insoluble product;) further, on account of consists of two constituents-name1y, of the their highly-acidic character, (they combine, 2o sulfonic-acid alkaline salts per se, soluble in for example, with nearly eight per cent. of

water, and of sulfone-like bodies per se, incalcium, while the product insoluble in wasoluble in Waterand that these latter bodies ter only contains two and one-half per cent. may be maintained in aqueous solution only of calcium,) and, finally, on account of the by the former-the sulfonic acid alkaline capability of their salts to conveysubstances 25 salts. insoluble in water, such as cresol, in far larger If the sulfonized product obtained by the quantity into an aqueous solution than the reaction of sulfuric acid upon sulfureted alkali salts, which correspond to the insoluhydrocarbons is neutralized with the oxid, ble alkaline-earth and other metallic salts. hydroxid, or carbonate of an alkaline earth The acids, as Wellas theirsalts, furthermore 30 or heavy metal, or if the salt of an alkaline possess strong reducing properties of such a earthy metal or metal proper is added to the capacity that the salts with an easily-reducisolution of the sulfonized product which is ble base, such as the silver or mercury salts, neutralized by means of an alkali, it yields a cannot be produced in a permanent form. precipitate which contains not only the above- In View of the great importance these salts 5 mentioned sulfone-like bodies per sc, insoluwould have in their strong antiseptical and ble in water, but also the total amount of the bactericidal effect attempts have been made sulfonic acids, as alkaline-earth or metal salt, to convert the acids in such a manner that respectively, since the sulfonicacids obtained permanent metallic salts could be obtained by the reaction of sulfuric acid upon sultherefrom. In the course of further experib 40 fureted hydrocarbons are formed with alkaments it has now been proven that the acids lineearth and heavymetal combinations giving soluble alkaline-earth salts will lose which are insoluble in water, as explained in their unsaturated character on treating the the specifications of my United States Patsame with oxidizing means and that these ents Nos. 624,027 and 624,028 and also in oxidized acids will, in fact, form permanent 5 45 German Patent No. 72,049. salts soluble in Water with heavy metals, even From a careful investigation recently perwith such metals the oxids of which are easily formed it has been proven that a considerable reducible. part of the sulfonic acids is not precipitated The following example may more fully elu by alkaline earth and heavy metals and that cidate the production of the permanent silver 50 therefore the sulfonized product also contains salt: One kilogram of the sulfonized product acids the alkaline earth and heavy metal obtained by the reaction of sulfuric acid upon Seefeld mineral oil is dissolved in about two to three liters of water, and this solution at a raised temperature is neutralized with carbonate of barium. the, brown-colored liquid is decanted from the. precipitate and evaporated to a small volume. The barium is precipitated from the solution by means of the calculated quantity of sulfuric acid and the filtrate now containing the sulfonic acid in solution, heated for some time with about 0.4 liter of commercial peroxid of hydrogen, (containing three per cent. H 0 The color of the liquid, at first green, soon turns into a reddish brown. The solution of the oxidized acid is then evaporated. The residual acid thus resulting forms a dark brown syrup-like nearly odorless'mass, which is easily soluble in water.

In order to produce the silver salt, the aqueous solution of the oxidized acid. is neutralized with argentic oxid or carbonate, then filtered from the undis 'solved constituents, and the filtrate dried by evaporation or otherwise. The residual silver salt appears as a brown mass, which is easily pulverized and readily soluble in water. Further experiments have shown that the same acid and permanent metal salts will also result from direct oxidation of the sulfonized product, which is obtained by treating sulfureted hydrocarbons with sulfuric acid. The aqueous solution of such oxidation product is then to be neutralized by means of the oxid,hydroxid, or carbonate of an alkaline earth or heavy metal and filtered off from the insoluble alkaline-earth or heavy-metal salts. The oxidized acid is now directly obtained by precipitating the base from the solution. The acid thus obtained and the salts resulting from neutralizing the former fully correspond to the products hereinbefore described. If, for instance, chromic acid is applied as oxidizing agent, the process will be as follows; One kilogram of the sulfonized product resulting from the reaction of sulfuric acid upon a sulfureted hydrocarbon is dissolved in about two liters of water, and to this solution is gradually added an aqueous solution of about fifty grams of chromic acid and forty grams of sulfuric acid. After the chromic acid is reduced the liquid standing above the precipitate is decanted off and, mixed with milk of lime in order to precipitate chromic oxid and sulfuric acid, whereupon the filtrate is evapand finally the spirit distilled from thefil- I trate. The aqueous solution now containing the free oxidized acid is neutralized with sil- Ver oxid. After the evaporation of the wa- After cooling this mixture ter, which is preferably performed in vacuo, the silver salt remains as a brown easilypulverizable residue, fully corresponding with the product obtained according to the firstmentioned example.

Having thus described myinvention, What I claim as new therein, and desire to secure by Letters Patent, is-

1. The process of producing sulfonic acids, forming permanent metallic salts soluble in water, which consists in neutralizing the sulfonized compound obtained by the action of sulfu ric acid on sulfureted hydrocarbons with a suitable metallic base, filtering off the liquid from the insoluble salts, oxidizing the filtered solution, setting free the sulfonic acid by precipitating the base, and evaporating the filtrate to dryness, substantially as described.

2. The process of producing permanent metallic salts soluble in water, which consists in neutralizing the sulfonized compound obtained by the action of sulfuric acid upon sulfureted hydrocarbons with an alkaline-earth base, filtering off the liquid from the insoluble salts, oxidizing the filtered solution, setting free the sulfonic acid by precipitating the alkaline earth, neutralizing the filtrate with a metallic base and evaporating the liquid to dryness, substantially as described.

The process of producing sulfonic acids, forming permanent metallic salts soluble in water, which consists in oxidizing the sulfonized compound obtained by the action of sulfuric acid on sulfureted hydrocarbons, neutralizing the oxidized product with a suitable metallic base, filtering'off the liquid from the precipitated insoluble salts, setting free the sulfoni'c acid by precipitating the base, and evaporating the filtrate to dryness, substantially as described.

at. The process of. producing permanent metal salts soluble in water, which consists in oxidizing the sulfonizedcompound obtained by the action of sulfuric acid on sulfureted hydrocarbons, neutralizing the oxidized product with an alkaline-earth base, filtering off the liquid from the precipitated insoluble salts, setting free the sulfonic acid by precipiztating the earth alkali, neutralizing the filtrate with a metallic base and evaporating the liquid to dryness, substantially as de scribed.

5. As a new product of manufacture, the

i herein-described sulfonic-acid salts, consisting of a metal proper and an oxidized sulfonic- 3 acid compound derived from sulfureted hydrocarbons combined with sulfuric acid,

which salts are ofa brown color, soluble in water and permanent in their solution.

LUDlVIG OTTO HELMERS. Witnesses:

ALEXANDER SPECHT, E. H. L. MUMMENHOFF.

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